CN103159968A - Method for bonding fluorine-silicon rubber layer and silicon rubber layer - Google Patents

Method for bonding fluorine-silicon rubber layer and silicon rubber layer Download PDF

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Publication number
CN103159968A
CN103159968A CN2011104068194A CN201110406819A CN103159968A CN 103159968 A CN103159968 A CN 103159968A CN 2011104068194 A CN2011104068194 A CN 2011104068194A CN 201110406819 A CN201110406819 A CN 201110406819A CN 103159968 A CN103159968 A CN 103159968A
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product
sio
group
silicon
siloxane
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CN103159968B (en
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王韶晖
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Dow Shanghai Holding Co Ltd
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Dow Corning China Holding Co Ltd
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Priority to CN201110406819.4A priority Critical patent/CN103159968B/en
Priority to JP2014545070A priority patent/JP6069342B2/en
Priority to KR1020147018208A priority patent/KR20140105511A/en
Priority to PCT/CN2012/084439 priority patent/WO2013082989A1/en
Priority to US14/363,406 priority patent/US9908308B2/en
Priority to EP12856103.2A priority patent/EP2788410B1/en
Publication of CN103159968A publication Critical patent/CN103159968A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a general shape other than plane
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/20—Layered products comprising a layer of natural or synthetic rubber comprising silicone rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/18—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only
    • B32B37/182—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of discrete sheets or panels only one or more of the layers being plastic
    • B32B37/185—Laminating sheets, panels or inserts between two discrete plastic layers
    • C—CHEMISTRY; METALLURGY
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
    • C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
    • C08J5/128—Adhesives without diluent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
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    • C08K5/14—Peroxides
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    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • F16L11/045—Hoses, i.e. flexible pipes made of rubber or flexible plastics with four or more layers without reinforcement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2250/24—All layers being polymeric
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    • B32—LAYERED PRODUCTS
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    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/72—Cured, e.g. vulcanised, cross-linked
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2305/77—Uncured, e.g. green
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2319/00—Synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
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    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
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    • C08J2383/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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    • C08J2483/04—Polysiloxanes
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    • C09J2483/00—Presence of polysiloxane
    • C09J2483/006—Presence of polysiloxane in the substrate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
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Abstract

The present invention relates to a method for bonding a fluorine-silicon rubber layer and a silicon rubber layer, and provides a method for bonding a fluorine-silicon rubber layer capable of being cured by using a non-hydrosilylation curing method and a perfluoroalkyl-free silicon rubber layer capable of being cured by using a non-hydrosilylation curing method. The method comprises the following steps: 1) before curing, adding a hydrosilylation catalyst or siloxane containing at least two silicon-bonded hydrogen groups to a fluorine-silicon rubber composition; 2) before curing, adding the hydrosilylation catalyst or the other siloxane containing at least two silicon-bonded hydrogen groups to a silicon rubber composition; 3) preparing a mixture containing the product from the step 1) and the product from the step 2), wherein a weight ratio of the product from the step 1) to the product from the step 2) is 40:60-60:40; 4) molding the product from the step 1), the product from the step 2) and the product from the step 3) into the desired shapes; 5) carrying out contact of the molded products in the step 4), and making the product from the step 3) position between the product from the step 1) and the product from the step 2); and 6) curing the product from the step 5) so as to bond the molded products under the contact condition.

Description

A kind of method that is used for the trifluoropropyl siloxane layer is bonded in silastic-layer
Technical field
The present invention relates to trifluoropropyl siloxane is bonded in improving one's methods of other silicon rubber, described trifluoropropyl siloxane can adopt non-hydrosilylation cure method to solidify, described other silicon rubber can adopt non-hydrosilylation cure method to solidify, and the invention still further relates to the product that uses described method preparation.
Background technology
Fluorosilicone rubber composition particularly based on those Fluorosilicone rubber compositions of the organopolysiloxane that comprises very most fluoro-alkyl, particularly perfluoroalkyl, can make it have that heat-resisting, cold-resistant, chemicals-resistant corrodes and the character of oil resistant after curing.Therefore these compositions are widely used in automobile and aircraft industry.But a subject matter of the trifluoropropyl siloxane of curing is, they can't with other base materials, as bonding well in rubber composition.
People have proposed the whole bag of tricks, be used for improving trifluoropropyl siloxane with based on the base material of other silicon rubber or the cementability of other substrate surfaces.These methods comprise that the material that will comprise a plurality of silicon-hydrogen bonds or a plurality of ethylene linkages adds in described trifluoropropyl siloxane and/or other silicon rubber to improve cementability.Can also add tackifier in described trifluoropropyl siloxane and/or other silicon rubber, for example based on the compound of cyanurate and/or isocyanuric acid ester, for example triallyl cyanurate or triallyl isocyanurate, but this may bring the problem of consistency aspect.
In US2008/0308227A, a kind of being used for trifluoropropyl siloxane layer and the bonding method of silastic-layer disclosed, described trifluoropropyl siloxane layer can use non-hydrosilylation cure method to solidify, and described silastic-layer does not contain perfluoroalkyl substantially.The method comprises the following steps:
I) before solidifying, hydrosilylation catalysts or the siloxanes that comprises the hydrogen group of at least two silicon bondings are added in described Fluorosilicone rubber composition; And
Ii) before solidifying, with described hydrosilylation catalysts or comprise another in the siloxanes of hydrogen group of at least two silicon bondings and add in described other rubber composition;
Iii) product with step (i) and step (ii) is shaped to required shape;
Iv) make the moulding product of step (iii) contact with each other; And
V) by carry out hydrosilylation reactions between it, make described moulding product bonding under the condition that is in contact with one another.
Summary of the invention
In first embodiment of the present invention, providing a kind of is used for trifluoropropyl siloxane layer and the bonding method of silastic-layer, described trifluoropropyl siloxane can use non-hydrosilylation cure method to solidify, described silastic-layer does not contain perfluoroalkyl substantially, can use non-hydrosilylation cure method to solidify, said method comprising the steps of;
I) before solidifying, hydrosilylation catalysts or the siloxanes that comprises the hydrogen group of at least two silicon bondings are added in described fluorosilicone rubber combination; And
Ii) before solidifying, with described hydrosilylation catalysts or comprise another in the siloxanes of hydrogen group of at least two silicon bondings and add in described other rubber composition;
Iii) preparation comprises the mixture of the product of step (i) and step (ii), and wherein the weight ratio of the product of the product of step (i) and step (ii) is 40: 60 to 60: 40;
Iv) product with step (i), step (ii) and step (iii) is configured as required shape;
V) moulding product with step (iv) contacts with each other, and the product of step (iii) is positioned between the product of the product of step (i) and step (ii); Vi) product of curing schedule (v), be bonded together described moulding product under the condition that contacts with each other.
One preferred embodiment in, the product of step (iii) keeps not being cured in step (vi) before.
Another preferred embodiment in, the product of the product of step (i), step (ii) and the product of step (iii) all keep not being cured in step (vi) before.
Another preferred embodiment in, (vi) exerts pressure to the interface between the product of step (iv) before and/or in process in step.
Another preferred embodiment in, step (vi) is carried out to being up at the temperature of 200 ℃ in room temperature.
Another preferred embodiment in, described hydrosilylation catalysts is based on the catalyzer of platinum metals, described catalyzer based on the platinum metals is selected from the catalyzer based on platinum, rhodium, iridium, palladium or ruthenium.
Another preferred embodiment in, the described siloxanes that comprises the hydrogen of silicon bonding is the linear structure with the hydrogen group of silicon bonding of comprising shown in following formula:
Me 3SiO(Me 2SiO) r[R”CH 2CH 2Si(Me)O] t(MeHSiO) zSiMe 3
In formula, each R " can be same or different; and expression comprises the side chain of 1-8 carbon atom or the perfluoroalkyl of straight chain; r is equal to or greater than zero; t and z are separately greater than zero; make fluorosiloxane copolymer comprise the siloxane unit of the hydrogen bonding of 1-10 % by mole; the fluorinated siloxane unit of at least 5 % by mole, the chain curing groups that the dimethyl siloxane units of surplus and following formula represent, wherein r is zero, t and z greater than zero, make fluorosiloxane copolymer comprise the fluorinated siloxane unit of 20-50 % by mole separately, are 10-10000mPa.s the viscosity of 25 ℃.
Another preferred embodiment in, the described siloxanes that comprises the hydrogen of silicon bonding comprises
HMe 2SiO(MeHSiO) m[R”QSi(Me)O] fSiMe 2H
HMe 2SiO(MeHSiO) m(R”QHSiO) fSiMe 2H
R”QMeHSiO(MeHSiO) m(R”QHSiO) fSiMeHRQ
Me 3SiO(Me 2SiO) 0.95m(MeHSiO) 0.05m(R”QMeSiO) fSiMe 3
HMe 2SiO(Me 2SiO) m(R”QMeSiO) fSiMe 2H
HMeR”QSiO(R”QMeSiO) fSiMeR”QH
Me 2R " QSiO (R " QMeSiO) 0.95f(R " QHiSiO) 0.05fWith
Me 3SiO(Me 2SiO) m(R”QMeSiO) 0.90f(R”QHSiO) 0.10fSiMe 3
Wherein, change in the scope of the colloid of the viscosity of polymkeric substance from the free flowing liquid to the sluggish flow, m and f are from zero to being equal to and greater than 10,000.
Another preferred embodiment in, described Fluorosilicone rubber composition comprises
(A) organopolysiloxane of 100 weight parts, the weight-average molecular weight of this organopolysiloxane comprise fluorinated siloxane unit and nonfluorinated siloxane unit greater than 100,000 in this polymkeric substance; The chemical formula of described fluorinated siloxane unit is (R " Q) a(R ') bSiO (4-a-b)/2, the chemical formula of described nonfluorinated siloxane unit is (R ') cSiO (4-c)/2In the described siloxane unit of fluoridizing with nonfluorinated; R " expression comprises the side chain of 1-8 carbon atom or the perfluoroalkyl of straight chain, Q represents by at least two carbon atoms described R " the group bivalent hydrocarbon radical, hydrocarbyl ether group or the hydrocarbon sulfide group that are connected with Siliciumatom; the univalence hydrocarbyl of the saturated or undersaturated silicon bonding of R ' expression, a=1-2 wherein, b=0-2; c=0-3
(B) the suitable filler of 5-200 weight part;
(E) fluorosiloxane copolymer, average each molecule of this fluorosiloxane copolymer comprises the hydrogen group of at least two silicon bondings; And
(C) organo-peroxide of 0.1-10 weight part,
(D) the second organopolysiloxane of 0-20 weight part, the weight-average molecular weight of this second organopolysiloxane are greater than 100,000, and the averaging unit chemical formula is R 1 ySiO (4-y)/2, R wherein 1Be that replace or unsubstituted univalence hydrocarbyl, this univalence hydrocarbyl can be undersaturated, but does not contain any fluoro substituents, and the span of y is between 1.96-2.03.
Another preferred embodiment in, the rubber composition that can adopt comprises:
(i) organopolysiloxane of the described any kind of component (E);
(ii) a kind of filler of the described any kind of component (B) or one group of filler;
(iii) solidifying agent of the described any kind of component (C);
(iV) hydrosilylation catalysts of the described any kind of component (F); And
Be selected from the optional additive of following one or more materials: rheology modifier, pigment, tinting material, release agent, softening agent, tackifier, whipping agent, fire retardant and siccative etc.
In second embodiment of the present invention, a kind of flexible pipe is provided, described flexible pipe comprises the trifluoropropyl siloxane bonding with silicon rubber by method preparation mentioned above.
Description of drawings
Fig. 1 has shown conventional turbo-supercharger flexible pipe.
Embodiment
In an embodiment of the invention, one or both in the product of the product of step (i) or step (ii) can be in step (vi) Procuring before.Perhaps, the product of the product of step (i) and step (ii) solidifies simultaneously with the product of step (iii) in step (vi).The product of step (iii) preferably keeps not being cured in step (vi) before.If necessary, can when being bonded together, three kinds of products exert pressure.This pressure can apply by mould, bandage or autoclave equipment.Between described trifluoropropyl siloxane product and described mixture compound at the interface and the reaction at the interface between described solid state si rubber product and described mixture can at room temperature carry out, perhaps carrying out under the highest approximately arbitrary temp of 200 ℃ from room temperature.
The silicon-fluorine polymer compositions that uses in step (i) can be any suitable Fluorosilicone rubber composition.
Preferably, described silicon-fluorine polymer compositions comprises following component
A) fluoridize the polydiorganosiloxane polymkeric substance;
B) one or more reinforcement and/or non-reinforcement filler;
C) suitable non-hydrosilylation cure catalyzer.
Preferably, described weight-average molecular weight of fluoridizing polydiorganosiloxane A is greater than 100,000, and/or be at least 10,000mPa.s the viscosity of 25 ℃, comprises fluorinated siloxane unit and optional nonfluorinated siloxane unit.Can use polystyrene standards, measure weight-average molecular weight by gel permeation chromatography (GPC).Described fluorinated siloxane unit preferably has following chemical formula
(R”Q) a(R′) bSiO (4-a-b)/2
In formula:
Each R " can be same or different, expression comprises the side chain of 1-8 carbon atom or the fluorinated alkyl of straight chain;
Each Q can be same or different, and expression comprises divalence hydrocarbon, hydrocarbyl ether or the hydrocarbon thioether of at least two carbon atoms.Each R " group is connected in Siliciumatom by the Q group,
Each R ' is same or different, the univalence hydrocarbyl of the optional saturated or undersaturated silicon bonding that replaces of expression,
A=0-2 wherein, b=0-2, in the time of a=0, each unit has at least a R ' group to comprise one or more carbon-fluorine bonds.
For the application, the one or more hydrogen atoms in " replacement " expression alkyl are replaced by another substituting group.Described substituent example includes but not limited to: halogen atom, for example chlorine, fluorine, bromine and iodine; The group of halogen atom, for example chloro methyl, perfluoro butyl, trifluoroethyl and nine fluorine hexyls; Sauerstoffatom; The group that contains Sauerstoffatom, for example (methyl) acrylic and carboxyl; Nitrogen-atoms; The group of nitrogen atom, for example amido functional group, acyl ammonia functional group and cyano functional group; Sulphur atom; And the group of sulfur atom-containing, for example sulfydryl.
The example of suitable saturated R ' group comprises C 1-C 10Alkyl, for example methyl, ethyl, propyl group, sec.-propyl, butyl, hexyl, 2-ethylhexyl, octyl group, iso-octyl and decyl.Preferably, in the time of a＞0, at least 90%, more preferably in fluorosiloxane copolymer except thiazolinyl all R ' groups be all methyl.Preferably, in the time of a=0, on average the nearly at least R ' in each unit comprises at least one carbon-fluorine bond, is most preferably CF 3-.
Preferably, in the four corner of 5-100 % by mole of fluorinated siloxane unit, R " expression comprises the fluoro-alkyl of 1-8 carbon atom.Each contained fluoro-alkyl comprise at least one-the C-F key.Each R " group can be same or different, can have conventional structure or branched structure.Preferably, at least a portion, most preferably at least 50% described fluorinated alkyl is perfluoroalkyl.Its example comprises CF 3-, C 2F 5-, C 3F 7-, CF for example 3CF 2CF 2-or (CF 3) 2CF-, C 4F 9-, CF for example 3CF 2CF 2CF 2-, (CF 3) 2CFCF 2-, (CF 3) 3C-and CF 3CF 2(CF 3) CF-; C 5F 11, CF for example 3CF 2CF 2CF 2CF 2-, C 6F 13-, CF for example 3(CF 2) 4CF 2-; C 7F 14-, CF for example 3(CF 2CF 2) 3-; And C 8F 17-.
Each perfluoroalkyl is by Q and silicon atom bonding, and described Q is the divalence spacer groups, and it comprises carbon, hydrogen and optional oxygen and/or sulphur atom, and described oxygen and/or sulphur atom are respectively the form of ether and thioether bond.If have sulphur atom and Sauerstoffatom, described sulphur atom and Sauerstoffatom must be only and carbon atom bonding.
Each Q group can have the arbitrary structures that comprises element mentioned above; But each Q group preferably has the C of conventional structure or branched structure 1-C 10Alkylidene group.The example of suitable alkylidene group comprises-CH 2CH 2-,-CH 2CH 2CH 2-,-CH (CH 3) CH 2-, (CH 2CH 2) 2-and-CH (CH 3) CH 2CH 2-.
Each fluorinated groups R " chemical formula of Q is preferably R " CH 2CH 2-.
Randomly, described fluoridize organopolysiloxane also comprise a certain proportion of, preferably less than unit sum in each molecule 25%, be more preferably less than 15% the nonfluorinated siloxane unit with following chemical formula
(R”’) cSiO (4-c)/2
In formula, R " ' univalence hydrocarbyl of the optional saturated or undersaturated silicon bonding that replaces of expression, c=0-3 wherein, but the mean value of preferred c is about 2.Each R " ' not fluorine-containing, so R " ' do not comprise the fluoro substituents that contains of mentioning in above " substituting group " General Definition.
R mentioned above " ' the optional saturated or undersaturated silicon bonding univalence hydrocarbyl that replaces of expression.Preferably, each R ' " can be same or different, be selected from C 1-C 10Alkyl; C 2-C 8Thiazolinyl, for example vinyl or allyl group; And/or aryl, for example phenyl, tolyl, benzyl, β-styroyl and styryl.In preferred each molecule, at least two R are arranged " ' substituting group is thiazolinyl, is most preferably vinyl.
In a preferred embodiment of the present invention, described fluorosiloxane copolymer comprises at least two thiazolinyls with 2-8 carbon atom, preferably vinyl.
The example of component A comprises the multipolymer of dimethylsilyl bis unit and (3,3,3-trifluoro propyl) methyl siloxy unit; The multipolymer of dimethylsilyl bis unit, (3,3,3-trifluoro propyl) methyl siloxy unit and vinyl methyl siloxy unit; The multipolymer of (3,3,3-trifluoro propyl) methyl siloxy unit and vinyl methyl siloxy unit; And poly-(3,3,3-trifluoro propyl) methylsiloxane.End group on its molecular chain is selected from trimethylsiloxy group, vinyl-dimethyl base siloxy, dimethyl hydroxyl siloxy and (3,3,3-trifluoro propyl) methyl hydroxyl siloxy.
Can use the combination (component (B)) of filler or the filler of any appropriate.These fillers can be the reinforcement fillers that uses separately, perhaps are combined with non-reinforcement filler.The reinforcement filler comprises abrasive silica, fumed silica, precipitated silica, aerosil, calcium carbonate.Non-reinforcement filler comprises wollastonite, quartz, kaolin, mica, pyrophyllite magnesiumcarbonate and other particle inoganic solids.
Component (B) can be added in described composition with that processed or untreated form.The filler of processing is with giving filler hydrophobic pretreatment, to promote the mixed process of filler/polymkeric substance.In some embodiments, filler is carried out in-situ treatment may be useful, in the case, in mixed process, treatment agent added composition of the present invention.Can use any suitable treatment agent.One or more below these treatment agents for example can comprise: silane, silazane or short chain organopolysiloxane polymer.Some suitable silane for example comprise: alkyltrialkoxysilaneand, for example Union carbide A-162, methyltrimethoxy silane; Phenyl trialkoxy silane, for example phenyltrimethoxysila,e; Perhaps thiazolinyl trialkoxy silane, for example vinyltriethoxysilane and vinyltrimethoxy silane.If necessary, can be with silazane as the agent of kaolin treatment of packing, for example hexamethyldisilazane; 1,1,3,3-tetramethyl-disilazane; And 1,3-divinyl tetramethyl-disilazane.The short chain organopolysiloxane can for example comprise that the polymerization degree is the hydroxy-end capped polydimethylsiloxane of 2-20, the polymerization degree is the hydroxy-end capped poly-diakyl alkyl alkenyl siloxane of 2-20, and the organopolysiloxane that comprises at least one Si-H group, described at least one Si-H group can be end group, can not be also end group.Poly-3,3, the 3-trifluoro propyl methylsiloxane of short-chain hydroxyl end-blocking.Fluoro-alkyl trialkoxy silane and fluoroalkyl silanes also can be used as treatment agent.
Preferred filler is the reinforcement filler, for example comprises fumed silica, precipitated silica, comprises rice husk ash, and calcium carbonate and/or the kaolin of certain grade.Can also use non-reinforcement filler, quartz, diatomite, barium sulfate, ferric oxide, titanium dioxide and carbon black, talcum, the wollastonite for example pulverized.Except above-mentioned filler, can use separately or comprise alumina, calcium sulfate (anhydrite), gypsum, calcium sulfate, magnesiumcarbonate with other fillers of above-mentioned filler and use, clay, for example kaolin, aluminium hydroxide, magnesium hydroxide (brucite), graphite, copper carbonate, malachite for example, nickelous carbonate, zaratite for example, barium carbonate, for example witherite and/or Strontium carbonate powder, for example strontianite.
The pH value of preferred described filler is less than 9.In addition, in order to obtain enough reinforcing effects, the specific surface area of described reinforced filling is preferably greater than 50 meters 2/ gram.For the component (A) of every 100 weight parts, the amount of described filler is the 5-200 weight part, preferred 20-80 weight part.If the amount of filler surpasses 200 weight parts, after processing and solidifying, described trifluoropropyl siloxane will lose its mechanical properties.
Any suitable organo-peroxide all can be used as component of the present invention (C).some organo-peroxides commonly used comprise benzoyl peroxide, 1, the 4-dichlorobenzoperoxide, 2, the 4-dichlorobenzoperoxide, 1, 4-dimethyl benzoyl peroxide, 2, 4-dimethyl benzoyl peroxide, ditertiary butyl peroxide, dicumyl peroxide, t-butylperoxyl benzoate, the monochloro benzoyl peroxide, ditertiary butyl peroxide, 2, 5-dimethyl-2, 5-pair-(tertiary butyl)-peroxide hexane, 1, 1-bis(t-butylperoxy)-3, 3, the 5-trimethyl-cyclohexane, tertiary butyl trimethylammonium superoxide, normal-butyl-4, 4-bis(t-butylperoxy) valerate, 1, 1-bis(t-butylperoxy)-3, 3, the 5-trimethyl-cyclohexane, t-butylperoxy sec.-propyl carbonic ether and t-butylperoxyl benzoate.Most suitable solidifying agent based on superoxide is benzoyl peroxide, 2,4-dichlorobenzoperoxide, ditertiary butyl peroxide and dicumyl peroxide.
This component can also form thickener by being dispersed in silicone oil.Recommendation is for the component (A) of every 100 weight parts, and the consumption of component (C) is the 0.1-10 weight part, preferred 0.5-2.0 weight part.
Described composition can also comprise 0-20 weight part (D) the second organopolysiloxane, and the weight-average molecular weight of this second organopolysiloxane is greater than 100,000, and the averaging unit chemical formula is R 1 ySiO (4-y)/2, R wherein yBe that replace or unsubstituted univalence hydrocarbyl, this univalence hydrocarbyl can also be undersaturated, for example comprises alkenyl or alkynyl, but does not contain any fluoro substituents, and the span of y is between 1.96-2.03.Can use polystyrene standards, measure weight-average molecular weight by gel permeation chromatography (GPC).For example, when component (A) is poly-(3,3, the 3-trifluoro propyl) when methylsiloxane, composition of the present invention can also mix with the optional component (D) of organopolysiloxane form, and the weight-average molecular weight of described component (D) is greater than 100,000, and do not contain 3,3,3-trifluoro propyl.The organic group of the silicon atom bonding in described organopolysiloxane is expressed as C 1-C 10Alkyl; C 2-C 8Thiazolinyl, for example vinyl or allyl group; And aryl, for example phenyl.Below the object lesson of these organopolysiloxane: the multipolymer of polydimethylsiloxane, polyvinyl methylsiloxane, dimethylsilyl bis unit and aminomethyl phenyl siloxy unit, and the multipolymer of dimethylsilyl bis unit and vinyl methyl siloxy unit.Recommend the consumption of described organopolysiloxane to meet the following conditions: after mixing, with respect to all univalence hydrocarbyls of silicon atom bonding, the content of 3,3,3-trifluoro propyl is at least 20 % by mole.
The basal component of Fluorosilicone rubber composition of the present invention is component (A), (B), (C) and optional (D).But, if necessary, mix following additive in said composition: softening agent, the two organo-siloxane oligopolymer of for example commonly using in rubber composition; Metallic soap or processing aid; Ferric oxide, titanium oxide, magnesium oxide, magnesiumcarbonate or oil resistant properties-correcting agent.The component of other that can comprise in composition of the present invention comprises chainextender, dyestuff, tinting material, pigment, viscosity modifier, bath life extender, inhibitor, solvent, fireproofing agent, releasing agent, whipping agent, fire retardant, conductive filler material and/or heat conductive filler, and siccative, processing aid, peroxide cure auxiliary agent, acid acceptor and UV stabilizer and toughner.Suitable fire retardant comprises for example halogenide, phosphate/ester and weisspiessglanz (III).Can also use thermo-stabilizer, for example cerium oxide and carbon black.
Fluorosilicone rubber composition of the present invention can be by the method preparation of any appropriate, for example in the conventional mixing equipment of two roller mills or kneader and so on, component (A)-(C) and component (D) (if present) are evenly mixed with required appropriate addn.Perhaps, can by under heating condition with component (A) and (B) pre-mixing, make the fluorine silicon rubber base compound, then it is mixed with component (C).
After the composition that makes solidified, the applicant found, the fluorosilicone of described curing shows excellent oil-proofness, and the binding property good with other the silicon rubber base material of curing.
The silicon rubber that is used for step (ii) is solid state si rubber (HCR) composition.Usually, the weight-average molecular weight of solid state si rubber (HCR) composition is greater than 100,000, and/or the viscosity of 25 ℃ greater than 1,000,000mPas.Can use polystyrene standards, measure weight-average molecular weight by gel permeation chromatography (GPC).Described silicon rubber can also comprise organic-silicon-modified organic rubber, described organic-silicon-modified organic rubber comprises any suitable organic rubber, such as isoprene-isobutylene rubber, ethylene-vinyl acetate rubber, terpolymer EP rubber (EPDM), paracril etc.
Usually, the solid state si rubber combination comprises organopolysiloxane polymer (A1), and it is R that this organosiloxane polymer (A1) comprises general formula aSiO 4-a/2The unit, wherein each R can be same or different, expression comprises the alkyl of 1-18 carbon atom, comprises the substituted hydrocarbon radical of 1-18 carbon atom, perhaps comprises the-oxyl of the highest 18 carbon atoms.Preferably, R is alkyl, thiazolinyl, aryl, alkaryl or the aralkyl that comprises the optional replacement of maximum 8 carbon atoms.Described alkyl can be for example methyl, ethyl, n-propyl, normal-butyl, sec-butyl and the tertiary butyl.Described thiazolinyl can be for example vinyl, allyl group, propenyl and butenyl.Described aryl and aralkyl can be for example phenyl, tolyl and benzoyl.Preferred group is methyl, ethyl, phenyl and vinyl.In preferred all R groups at least 80% is methyl or phenyl, most preferable.Preferred organopolysiloxane is those that meet the following conditions: wherein except the end group unit in fact a of all unit all equal 2, described siloxanes is linear polymer on substantially.Described organopolysiloxane can be millions of mPa.s the viscosity of 25 ℃, usually they is called colloid in the case, because they are not easy to flow, Just because of this, can define with plasticity-.
Solid rubber composition mentioned above also comprises filler (B1) and suitable catalyzer (C1) usually.Usually, (B1) and (C1) with above about the described component of fluorosilicone rubber combination (B) and (C) identical.Described rubber composition can also comprise above about the described identical additive of choosing wantonly arbitrarily of fluorosilicone rubber combination.
Described solid state si rubber combination can be by the method preparation of any appropriate, for example in the conventional mixing equipment of two roller mills or kneader and so on, component (A1)-(C1) and suitable additive (if necessary) are evenly mixed.Perhaps, can by under heating condition with component (A1) and (B1) pre-mixing, make silicon rubber basis compound, then with itself and component (C1) merging.
The inventor finds, so to adding siloxanes (hereinafter being called component (E)) with at least two hydrogen bonding by silicon groups in which kind of composition, adding hydrosilylation catalysts (hereinafter being called component (F)) there is no priority, prerequisite are not have which kind of composition to comprise simultaneously described siliconization catalyzer with at least two hydrogen bonding by silicon groups in which kind of composition.Therefore, when component (E) adds in described rubber composition, need add component (F) in trifluoropropyl siloxane, vice versa.
Any suitable siloxanes that comprises the hydrogen group of at least two silicon bondings can be as component (E) in described Fluorosilicone rubber composition or solid state si rubber combination.Amount with hydrogen atom silicon atom bonding in component (E) is equal to or greater than 0.2 % by weight, preferably is equal to or greater than 0.4 % by weight.As the amount of the hydrogen atom of the silicon bonding in fruit component (E) less than 0.2 % by weight, can variation with the binding property of base material.
In component (E), the group except the hydrogen atom of silicon bonding is expressed as univalence hydrocarbyl replacement or unsubstituted, for example C 1-C 6Alkyl; Aryl, for example phenyl; And full-fluorine group, for example 3,3,3-trifluoro propyl and/or 1,1,1,2,2,3,3,4,4 ,-nine fluorine hexyls.The molecular structure that component (E) has straight chain or ring-type usually, but can be also part branching or three-dimensional structure.The polymerization degree of preferred ingredient (E) is greater than 5, preferably in the scope of 10-150.
It is below the example of component (E): polymethyl hydrogen siloxane; The multipolymer of methyl hydrogen siloxy units and dimethylsilane oxygen base unit; And the multipolymer of methyl hydrogen siloxy units, dimethylsilane oxygen base unit and perfluoroalkyl (for example 3,3,3-trifluoro propyl and/or 1,1,1,2,2,3,3,4,4 ,-nine fluorine hexyls) methyl-silicane oxygen base unit.The end group of the molecular chain of component (E) is trimethylsiloxy or dimethyl hydrogen siloxy-.The content of preferred ingredient (E) is: the silastic polymer of every 100 weight parts is corresponding to the 0.01-10 weight part.Component (E) can not contain the unsaturated group of thiazolinyl hydrocarbon or alkynes class.
Preferably, when comprising component (E) in described solid state si rubber combination, described component (E) does not contain any fluorine-containing group.
When described component (E) was included in described Fluorosilicone rubber composition, component (E) can comprise perfluoroalkyl, but not necessarily comprised perfluoroalkyl.But, may preferably add the component (E) that comprises perfluoroalkyl in Fluorosilicone rubber composition, this is that component (E) may have higher consistency with Fluorosilicone rubber composition because if there are these groups.
The optional component (E) that comprises one or more fluoroalkyls can comprise that average each molecule comprises the fluorosiloxane copolymer of the hydrogen group of at least two silicon bondings.
Preferably, the benchmark that adds up in the siloxane unit in described fluorosiloxane copolymer, component (E) also comprises the fluoro siloxane unit of at least 2 % by mole, and in described polymkeric substance, all remaining siloxane units are all the siloxane units of non-fluoro; The chemical formula of described fluoro siloxane unit is (R " Q) (R 2) x(H) eSiO (3-x-e)/2, the chemical formula of the siloxane unit of described non-fluoro is (R 2) g(H) dSiO (4-g-d)/2, in the siloxane unit of described fluoro and non-fluoro, R ", Q's is described as defined above, R 2Expression does not contain the univalence hydrocarbyl of the silicon bonding of aliphatic unsaturated group, x=0-2, e=0-2, x+e=0-2, g=0-3, d=0-3 and g+d=0-3.
The component based on fluorosilicone (E) that is used for Fluorosilicone rubber composition of the present invention is the main organopolysiloxane that is comprised of hydrogen group, fluoro siloxane unit and the optional non-fluoro siloxane unit of silicon bonding.
In component (E), the siloxane unit of fluoro represents to comprise suitably the siloxane polymeric unit with the perfluoroalkyl of silicon atom bonding.The chemical formula of described fluoro siloxane unit is (R " Q) (R 2) x(H) eSiO (3-x-e)/2, its general example comprises that chemical formula is (R " Q) (R 2) x(H) eSiO 1/2The chain termination siloxane unit, x+e=2 wherein, for example (R " Q) (R ') 2SiO 1/2, (R " Q) (H) 2SiO 1/2(R " Q) (R 2) (H) SiO 1/2, chemical formula is (R " Q) (R 2) SiO 2/2(R " Q) be SiO (H) 2/2The chain extension siloxane unit, and chemical formula is (R " Q) SiO 3/2The chain branching siloxane unit.Perhaps, component C can be (R " Q) 2(R 2) x(H) eSiO (1-x-e)/2, wherein x and e all=0-1, and x+e=0-1.
Each fluorinated groups R " chemical formula of Q is preferably R " CH 2CH 2-, for component (E), requiring R " size of group is no more than CF 3CF 2CF 2CF 2-group is so that fluorosiloxane copolymer provides required bond property when solidifying in composition of the present invention.Therefore, the fluorosiloxane copolymer that is used for curable compositions of the present invention preferably comprises above-described fluoro siloxane unit, wherein R " structure of Q group is CF 3CF 2CF 2CF 2Q-, most preferably CF 3CF 2CF 2CF 2CH 2CH 2-or (CF 3) 2CFCH 2CH 2CH 2-.
If there is the nonfluorinated siloxane unit, its chemical formula is (R " ') g(H) dSiO (4-g-d)/2, its general example comprises that chemical formula is (R " ') g(H) dSiO 1/2The chain termination siloxane unit, wherein the g+d sum is 3, for example chemical formula is (R " ') 3SiO 1/2, (R " ') 2(H) SiO 1/2, (R " ') (H) 2SiO 1/2(H) 3SiO 1/2, the chain extension siloxane unit, wherein the c+d sum is 2, for example chemical formula is (R " ') 2SiO 2/2, and (R " ') (H) SiO 2/2(H) 2SiO 2/2The chain branching siloxane unit, wherein the g+d sum is 1 or 0, for example (R " ') SiO 3/2, (H) SiO 3/2And SiO 4/2Should be appreciated that each R 2And R " ' can be identical group.
R is discussed as preamble 2Expression does not contain the monovalent hydrocarbon group of the silicon bonding of aliphatic unsaturated group.Preferably, each R 2Can be same or different, the univalence hydrocarbyl of expression silicon bonding preferably comprises 1-10 carbon atom.Suitable R 2The example of group comprises alkyl, for example methyl, ethyl, propyl group, sec.-propyl, butyl, hexyl, 2-ethylhexyl, octyl group, iso-octyl and decyl; Aryl, for example phenyl, tolyl, benzyl, beta-phenyl ethyl and styryl.In preferred described fluorosiloxane copolymer at least 90%, more preferably whole R 2Group is all methyl.
Although the viscosity of component (E) can be up to millions of mPa.s (the viscosity of 25 ℃), if think that it can not be nonfluid that described polymkeric substance needs, example gel or solid.Therefore, if there is described chain branching siloxane unit, should only comprise a small amount of chain branching siloxane unit.
The object lesson of the siloxane unit of described selection includes but not limited to Me 3SiO 1/2, Me 2HSiO 1/2, R " and QMe 2SiO 1/2, R " and QMeHSiO 1/2, Me 2SiO 2/2, MeHSiO 2/2, R " and QMeSiO 2/2And R " QHSiO 2/2, R wherein for example " and be perfluoro butyl.
When comprising fluorin radical, the general example of preferred component (E) includes but not limited to following group when component (E):
HMe 2SiO(MeHSiO) m[R”QSi(Me)O] fSiMe 2H
HMe 2SiO(MeHSiO) m(R”QHSiO) fSiMe 2H
R”QMeHSiO(MeHSiO) m(R”QHSiO) fSiMeHRQ
Me 3SiO(Me 2SiO) 0.95m(MeHSiO) 0.05m(R”QMeSiO) fSiMe 3
HMe 2SiO(Me 2SiO) m(R”QMeSiO) fSiMe 2H
HMeR”QSiO(R”QMeSiO) fSiMeR”QH
Me 2R " QSiO (R " QMeSiO) 0.95f(R " QHiSiO) 0.05fWith
Me 3SiO(Me 2SiO) m(R”QMeSiO) 0.90f(R”QHSiO) 0.10fSiMe 3
Wherein, change in the scope of the colloid of the viscosity of polymkeric substance from the free flowing liquid to the sluggish flow, the value of m and f is from zero to being equal to and greater than 10,000.
Preferably, any fluorine component (E) has the linear structure that contains the hydrogen bonding by silicon group that following formula represents:
Me 3SiO(Me 2SiO) r[R”CH 2CH 2Si(Me)O] t(MeHSiO) zSiMe 3
In formula, the value of r is equal to or greater than zero, t and z value separately is all greater than zero, make described fluorosiloxane copolymer comprise the siloxane unit of the hydrogen bonding of 1-95 % by mole, the fluoro siloxane unit of at least 5 % by mole and the dimethyl siloxane units of surplus, and be 10-10000mPa.s the viscosity of 25 ℃.
In the formula of above siloxane unit, x, e, g and d represent integer, their value is as described herein.
This area is well-known, the m of described straight chain fluorosiloxane copolymer, and f, r, the value representation mean value of t and z makes described polymkeric substance comprise the fluoro siloxane unit of aequum, has required viscosity at 25 ℃.Therefore, m, f, m+f, r, t, the value of z and r+t+z can change a lot according to the structure of fluoro siloxane unit content, fluoro group and the viscosity of polymkeric substance.Along with the molecular fraction of the fluoro siloxane unit in polymkeric substance and/or the wherein size increase of fluoro group, the viscosity of described polymkeric substance increases thereupon.
Although r, the value of t and z can minimum be the mark that value that the value of 1, r and t can be equal to or greater than 10,000, z is defined as the r+t+z sum usually, for example 1/100 of the r+t+z sum to 2/10.
Most preferred fluorine component (E) is the methyl perfluoroalkyl methyl hydrogen siloxane of trimethylsiloxy group end-blocking.Most preferably, described perfluoroalkyl is perfluoro butyl ethyl etc.
The content of preferred ingredient (E) is: the component of every 100 weight parts (A) is corresponding to the 0.01-10 weight part.Less than 0.01 weight part, can not provide improvement to curing properties and bond property as the content of fruit component (E).
Therefore, when described Fluorosilicone rubber composition comprises component (E), can comprise
(A) organopolysiloxane of 100 weight parts, the weight-average molecular weight of this organopolysiloxane comprise fluorinated siloxane unit and nonfluorinated siloxane unit greater than 100,000 in this polymkeric substance; The chemical formula of described fluorinated siloxane unit is (R " Q) a(R ') bSiO (4-a-b)/2, the chemical formula of described nonfluorinated siloxane unit is (R ') cSiO (4-c)/2In the described siloxane unit of fluoridizing with nonfluorinated; R " expression comprises the side chain of 1-8 carbon atom or the perfluoroalkyl of straight chain, Q represents by at least two carbon atoms described R " the group bivalent hydrocarbon radical, hydrocarbyl ether group or the hydrocarbon sulfide group that are connected with Siliciumatom; the univalence hydrocarbyl of the saturated or undersaturated silicon bonding of R ' expression, a=1-2 wherein, b=0-2; c=0-3
(B) the suitable filler of 5-200 weight part;
(E) fluorosiloxane copolymer, average each molecule of this fluorosiloxane copolymer comprises the hydrogen group of at least two silicon bondings; And
(C) organo-peroxide of 0.1-10 weight part,
(D) the second organopolysiloxane of 0-20 weight part, the weight-average molecular weight of this second organopolysiloxane are greater than 100,000, and the averaging unit chemical formula is R 1 ySiO (4-y)/2, R wherein 1Be that replace or unsubstituted univalence hydrocarbyl, this univalence hydrocarbyl can be undersaturated, but does not contain any fluoro substituents, and the value of y is between 1.96-2.03.
The applicant finds, by add component (F) in the present composition that does not contain component (E), can improve the binding property of fluorosiloxane copolymer of the present invention and described solid state si rubber combination.Think by adding described hydrosilylation catalysts to cause reaction with component (E), thereby significantly improved two kinds of cured products binding property each other.
Although the preferred described polymkeric substance that comprises the hydrogen group of silicon bonding is included in described Fluorosilicone rubber composition, but this point is not crucial part, described hydrosilylation catalyst can form the part of described Fluorosilicone rubber composition, also can add the silicone compounds of the suitable hydrogen atom that comprises the silicon bonding in described solid state si rubber combination.
Can use any suitable hydrosilylation catalysts.Described hydrosilylation catalysts is preferably based on the catalyzer of platinum metals, and described catalyzer based on the platinum metals is selected from the catalyzer based on platinum, rhodium, iridium, palladium or ruthenium.The catalyzer that comprises the platinum metals that can be used for present composition catalytic curing can be known can catalysis silicon bonding hydrogen atom and any catalyzer of the reaction between the thiazolinyl of silicon bonding.The platinum metals that is preferred for the catalyzer that the present composition solidifies by hydrosilylation is platinum.Some platinum base hydrosilylation catalysts that are preferred for present composition curing are platinum, platinic compound and platinum complex.Representational platinic compound comprises Platinic chloride, six hydration Platinic chlorides, platinum dichloride, and these compounds comprise the title complex that small molecular weight contains vinylic organosiloxane.Other the hydrosilylation catalysts of the present invention that is suitable for comprises for example rhodium catalyst, for example [Rh (O 2CCH 3) 2] 2, Rh (O 2CCH 3) 3, Rh 2(C 8H 15O 2) 4, Rh (C 5H 7O 2) 3, Rh (C 5H 7O 2) (CO) 2, Rh (CO) [Ph 3P] (C 5H 7O 2), RhX 3[(R 3) 2S] 3, (R 4 3P) 2Rh (CO) X, (R 4 3P) 2Rh (CO) H, Rh 2X 2Y 4, H aRh bAlkene cCl d, Rh (O (CO) R 3) 3-n(OH) n, wherein X is hydrogen, chlorine, bromine or iodine, Y is alkyl, for example methyl or ethyl, CO, C 8H 14Or 0.5C 8H 12, R 3Alkyl, cycloalkyl or aryl, R 4The group that alkyl, aryl or oxygen replace, a be 0 or 1, b be 1 or 2, c be the integer of 1-4, comprise end value, d be 2,3 or 4, n be 0 or 1.Can also use any suitable iridium catalyst, for example Ir (OOCCH 3) 3, Ir (C 5H 7O 2) 3, [Ir (Z) (En) 2] 2Or (Ir (Z) (diene)] 2, wherein Z is chlorine, bromine, iodine or alkoxyl group, and En is alkene, and diene is cyclooctadiene.
Component (F) can be added in composition of the present invention with the amount that is equivalent to following consumption: each composition of 1,000,000 parts, corresponding to the element state platinum metals of minimum 0.001 weight part.Preferably, the concentration of the platinum metals in described composition can provide following equivalent: the element state platinum metals of 1ppm at least.Usually the concentration of preferred catalyst can be equivalent to provide the element state platinum metals of about 3-50ppm.
The mixture that is used for step (iii) comprises the Fluorosilicone rubber composition of step (i) and the solid state si rubber combination of step (ii).Described mixture can by any suitable method preparation, for example in the conventional mixing equipment of two roller mills or kneader and so on, evenly mix two kinds of rubber combinations.In described blend composition, the ratio of described Fluorosilicone rubber composition and solid state si rubber combination should be 40: 60 to 60: 40.If ratio of mixture can variation with the binding property of base material beyond the scope of 40: 60 to 60: 40.
The applicant finds, such mixture compounding can shockingly improve the binding property with the silicon rubber base material of the trifluoropropyl siloxane base material that solidifies and curing.
The present invention can be used for any fusible situation that needs to improve between above-mentioned two layers, and is used for the fluorosilicone rubber combination in the situation that will improve oil-proofness of what is the need in office.A kind of purposes relevant to these two kinds possible application is to make the parts that are used for automobile, for example turbo-supercharger flexible pipe.
The turbo-supercharger flexible pipe that has shown a kind of routine in Fig. 1.Turbo-supercharger flexible pipe (1) shown in Figure 1 comprises inner fluorosilicone lining (2), mixolimnion (3), solid state si rubber inner layer (4), usually by suitable reinforced fabric for example enhancement layer (5) and the solid state si rubber outer (6) of aromatic polyamide and so on preparation
Present invention is described below with reference to embodiment:
Embodiment
The trifluoropropyl siloxane that is used for following examples comprises following component (all values are weight part):
FSR composition 1
The hydroxy-end capped trifluoro propyl methylsiloxane vinyl methylsiloxane multipolymer of 67 weight parts, by the GPC (toluene solution of 1 % by weight, RI detector, polystyrene standards) recording its weight-average molecular weight is 610,000 (contents of ethylene: 0.13 % by weight)
The fumed silica of 23 weight parts
The hydroxy-end capped trifluoro propyl methylsiloxane of 8 weight parts
0.3 the dimethyl methyl vinylsiloxane of the dimethyl vinyl siloxy end-blocking of weight part
1.8 the methyl of the trimethyl silyl end-blocking of weight part (perfluoro butyl ethyl) siloxanes methylhydrogensiloxacopolymer copolymer, its viscosity at 25 ℃ is 35mm 2/ s (SiH content: 0.5 % by weight)
1 % by weight contain 45% 2,5-dimethyl-2, the silicone oil pasty mixture of 5-two (t-butyl peroxy) hexane catalyzer.
Solid state si rubber combination used has following composition:
HCR1
The dimethyl siloxane methyl ethylene silicone copolymers of the dimethyl vinyl siloxy end-blocking of 62 weight parts, by the GPC (tetrahydrofuran solution of 0.1 % by weight, the reference RI-detector, use polystyrene standards to build typical curve and carry out gpc analysis) to record its weight-average molecular weight be 680,000 (contents of ethylene: 0.02 % by weight)
The dimethyl siloxane methyl ethylene silicone copolymers of the dimethyl vinyl siloxy end-blocking of 1 weight part, its viscosity at 25 ℃ are 17000mPas (contents of ethylene: 7.8 % by weight)
31.4 the fumed silica of weight part
The hydroxy-end capped dimethyl siloxane of 5 weight parts, viscosity is about 21mPa.s.
0.4 the hydroxy-end capped dimethyl siloxane methyl ethylene silicone copolymers of weight part, its viscosity at 25 ℃ are 20mPas (contents of ethylene: 10 % by weight)
0.2 the mixture of the following component of weight part: 1,3-divinyl-1,1,3, dimethyl siloxane methyl ethylene silicone copolymers (the platinum content: 0.5 % by weight) of 3-tetramethyl disiloxane platinum complex and dimethyl vinyl siloxy end-blocking
1 % by weight contain 45% 2,5-dimethyl-2, the silicone oil pasty mixture of 5-two (t-butyl peroxy) hexane catalyzer.
Unless otherwise indicated, described platinum catalyst comprises the platinum and 1,3 that accounts for composition 0.5 % by weight ,-divinyl-1,1,3, the title complex of 3-tetramethyl disiloxane.
Sample preparation
Unless opposite explanation is arranged, otherwise all samples that the test of the binding property described in following examples is used is all to use the following methods preparation :-
The mixture compacting of trifluoropropyl siloxane, solid state si rubber and trifluoropropyl siloxane and solid state si rubber is formed the uncured thin slice that is of a size of 1 millimeter of 150x 150x.Then they are fit together, simultaneously the PET film is inserted between described synusia from an end, in order to make its separation after solidifying.Then make the sheet material of applying at 170 ℃, solidified in the mould of 2 millimeters deep 10 minutes, then in air oven, 200 ℃ of regelates 4 hours.Then use suitable parting tool to cut out the standard batten of 25 mm wides, analyze in the specimen of gained the level of adhesion between two lamellas.
The binding property test
Use the Instron tester for elongation, under the pinblock draw speed of 50 mm/min, the sample for preparing in embodiment is carried out 180 ° peel off test.
Embodiment 1
In this embodiment, mixture uncured and preformed trifluoropropyl siloxane (FSR) and solid state si rubber (HCR) sample and HCR and FSR is fitted, then use above sample preparation methods to be cured, make the sample of various compounds solidify also bonded to each other according to an embodiment of the invention.By according to the described ratio of table 1, evenly mix the mixture of preparation HCR and FSR with two roller mills.
Table 1
Figure BDA0000117517590000171
As can be seen from Table 1, in the situation that ratio of mixture is 60: 40 to 40: 60, bonding between the biased sample of HCR and FSR and HCR layer and FSR layer all obtained the significantly improved reactive force result of peeling off.
Table 2 has shown HCR, the physicals of FSR and their mixture (the mixed weight ratio is in the situation of 50: 50).All physical testings all adopt with hereinafter described identical method and carry out:
Table 2

Claims (11)

1. one kind is used for trifluoropropyl siloxane layer and the bonding method of silastic-layer, described trifluoropropyl siloxane can use non-hydrosilylation cure method to solidify, described silastic-layer does not contain perfluoroalkyl, and can use non-hydrosilylation cure method to solidify, and said method comprising the steps of;
I) before solidifying, hydrosilylation catalysts or the siloxanes that comprises the hydrogen group of at least two silicon bondings are added in described Fluorosilicone rubber composition;
Ii) before solidifying, with described hydrosilylation catalysts or comprise another in the siloxanes of hydrogen group of at least two silicon bondings and add in described rubber composition;
Iii) preparation comprises the mixture of the product of step (i) and step (ii), and wherein, the weight ratio of the product of the product of step (i) and step (ii) is 40: 60 to 60: 40;
Iv) product with step (i), step (ii) and step (iii) is shaped to required shape;
V) moulding product with step (iv) contacts with each other, and the product of step (iii) is positioned between the product of the product of step (i) and step (ii);
Vi) by the product of curing schedule (v), described moulding product is bonded together under the condition that contacts with each other.
2. the method for claim 1, is characterized in that, the product of described step (iii) keeps not being cured in step (vi) before.
3. the method for claim 1, is characterized in that, the product of the product of step (i), step (ii) and the product of step (iii) all keep not being cured in step (vi) before.
4. the method for claim 1, is characterized in that,, exerted pressure in the interface between the product of step (iv) before and/or in process in step (vi).
5. the method for claim 1, is characterized in that, step (vi) is being carried out to being up at the temperature of 200 ℃ from room temperature.
6. the method for claim 1, is characterized in that, described hydrosilylation catalysts is based on the catalyzer of platinum metals, and described catalyzer based on the platinum metals is selected from the catalyzer based on platinum, rhodium, iridium, palladium or ruthenium.
7. the method for claim 1, is characterized in that, the described siloxanes that comprises the hydrogen of silicon bonding is the linear structure with hydrogen group of the silicon bonding shown in following formula:
Me 3SiO(Me 2SiO) r[R”CH 2CH 2Si(Me)O] t(MeHSiO) zSiMe 3
In formula, each R " can be same or different; and expression comprises the side chain of 1-8 carbon atom or the perfluoroalkyl of straight chain; r is equal to or greater than zero; t and z are separately greater than zero; make fluorosiloxane copolymer comprise the siloxane unit of the hydrogen bonding of 1-10 % by mole; the fluorinated siloxane unit of at least 5 % by mole, the chain curing groups that the dimethyl siloxane units of surplus and following formula represent, wherein r is zero, t and z greater than zero, make fluorosiloxane copolymer comprise the fluorinated siloxane unit of 20-50 % by mole separately, are 10-10000mPa.s the viscosity of 25 ℃.
8. method as claimed in claim 7, is characterized in that, the described siloxanes that comprises the hydrogen of silicon bonding comprises:
HMe 2SiO(MeHSiO) m[R”QSi(Me)O] fSiMe 2H
HMe 2SiO(MeHSiO) m[R”QSi(Me)O] fSiMe 2H
R”QMeHSiO(MeHSiO) m(R”QHSiO) fSiMeHRQ
Me 3SiO(Me 2SiO) 0.95m(MeHSiO) 0.05m(R”QMeSiO) fSiMe 3
HMe 2SiO(MeHSiO) m[R”QSi(Me)O] fSiMe 2H
HMeR”QSiO(R”QMeSiO) fSiMeR”QH
Me 2R " QSiO (R " QMeSiO) 0.95f(R " QHiSiO) 0.05fWith
Me 3SiO(Me 2SiO) m(R”QMeSiO) 0.90f(R”QHSiO) 0.10fSiMe 3
Wherein, change in the scope of the colloid of the viscosity of polymkeric substance from the free flowing liquid to the sluggish flow, m and f are from zero to being equal to and greater than 10,000.
9. the method for claim 1, is characterized in that, described Fluorosilicone rubber composition comprises
(A) organopolysiloxane of 100 weight parts, the weight-average molecular weight of this organopolysiloxane comprise fluorinated siloxane unit and nonfluorinated siloxane unit greater than 100,000 in this polymkeric substance; The chemical formula of described fluorinated siloxane unit is (R " Q) a(R ') bSiO (4-a-b)/2, the chemical formula of described nonfluorinated siloxane unit is (R ') cSiO (4-c)/2In the described siloxane unit of fluoridizing with nonfluorinated; R " expression comprises the side chain of 1-8 carbon atom or the perfluoroalkyl of straight chain, Q represents by at least two carbon atoms described R " the group bivalent hydrocarbon radical, hydrocarbyl ether group or the hydrocarbon sulfide group that are connected with Siliciumatom; the univalence hydrocarbyl of the saturated or undersaturated silicon bonding of R ' expression, a=1-2 wherein, b=0-2; c=0-3
(B) the suitable filler of 5-200 weight part;
(E) fluorosiloxane copolymer, average each molecule of this fluorosiloxane copolymer comprises the hydrogen group of at least two silicon bondings; And
(C) organo-peroxide of 0.1-10 weight part,
(D) the second organopolysiloxane of 0-20 weight part, the weight-average molecular weight of this second organopolysiloxane are greater than 100,000, and the averaging unit chemical formula is R 1 ySiO (4-y)/2, R wherein 1Be that replace or unsubstituted univalence hydrocarbyl, this univalence hydrocarbyl can be undersaturated, but does not contain any fluoro substituents, and the span of y is between 1.96-2.03.
10. according to any one of the preceding claims method, is characterized in that, the described rubber composition of employing comprises
(i) organopolysiloxane of the described any kind of the component in claim 9 (E); (ii) a kind of or one group of filler of the described any kind of the component in claim 9 (B); (iii) solidifying agent of any kind of the component in claim 9 (C) definition; And
Be selected from the optional additive of following one or more materials: rheology modifier, pigment, tinting material, release agent, softening agent, tackifier, whipping agent, fire retardant and siccative.
11. a flexible pipe, it comprises by the bonding trifluoropropyl siloxane of the described method of any one and silicon rubber in claim 1-10.
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